Monoazo dyes with cyclic amine as fluorescence quenchers

A compound having the formula:

• wherein at least one of R1 or R2 is a nitro group;
• X is O, S, or NR17, wherein R17 is H, an alkyl group that is saturated or unsaturated, linear or branched, unsubstituted, or further substituted by F, Cl, Br, I, CN, OH, alkenyl, alkynyl, alkylcarbonyl, amide, thioamide, or Q, or an aryl group optionally substituted by F, Cl, Br, I, CN, OH, alkenyl, alkynyl, alkylcarbonyl, amide, thioamide, or Q,
• Q is a carboxyl group (CO2−), a carbonate ester (COER12), a sulfonate ester (SO2ER12), a sulfoxide (SOR12), a sulfone (SO2CR12R13R14) a sulfonamide (SO2NR12R13), a phosphate (PO4−), a phosphate monoester (PO3−ER12), a phosphate diester (PO2NR12R13), a phosphonate (PO3−) a phosphonate monoester (PO2−ER12) a phosphonate diester (POER12ER13), a thiophosphate (PSO3−), a thiophosphate monoester (PSO2−ER12) a thiophosphate diester (PSOER12ER13), a thiophosphonate (PSO2−), a thiophosphonate monoester (PSO−ER12) a thiophosphonate diester (PSER12ER13), a phosphonamide (PONR12R13NR15R16), its thioanalogue (PSNR12R13NR15R16) a phosphoramide (PONR12R13NR14NR15R16), its thioanalogue (PSNR12R13NR14NR15R16), a phosphoramidite (PO2R15NR12R13) or its thioanalogue (POSR15NR12R13), wherein E is independently O or S;
• R1, R2, R6, R7, R8, and R9 are each independently H, F, Cl, Br, I, CN, nitro, azido, hydroxyl, amino, hydrazine, aryl, aroxyl, alkenyl, alkynyl, alkyl, alkoxy, alkylamino, dialkylamino, arylamino, diarylamino, alkylamino, alkylarylamino, alkanoylamino, alkylthio, alkylcarbonyl, aryl carbonyl, alkylthiocarbonyl, arylthiocarbonyl, alkyloxycarbonyl, aroxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl, dialkylaminocarbonyl, diarylaminocarbonyl, alkyl(aryl)aminocarbonyl, arylcarboxamido, or Q, wherein the alkyl or alkoxy groups are saturated or unsaturated, linear or branched, unsubstituted or further substituted by F, Cl, Br, I, CN, OH, alkenyl, alkynyl, alkylcarbonyl, amide, thioamide, or Q, and the aryl group is optionally substituted by F, Cl, Br, I, CN, OH, alkenyl, alkynyl, alkylcarbonyl, amide, thioamide, or Q;
• one or more of R1 in combination with R17, R6 in combination with R7, and R8 in combination with R9 form a saturated or unsaturated 5- to 10-member ring optionally substituted by one or more of a saturated or unsaturated, linear or branched, substituted or unsubstituted alky group, aryl, alkenyl, alkynyl, a saturated or unsaturated, branched or linear, substituted or unsubstituted alkoxy group, aroxyl, hydroxyl, F, Cl, Br, I, CN, nitro, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, carbonyl, thiocarbonyl, carboxylic acid, thiocarboxylic acid, carboxylic acid ester, thiocarboxylic acid ester, nitro, amino, amide, thioamide, azido, hydrazino, phosphonate or thiophosphonate, wherein the aryl group is optionally substituted with F, Cl, Br, I, CN, OH, alkyl, alkenyl, alkynyl, alkoxy, aryoxy, alkylthio, arylthio, nitro, azido, hydrazino, carboxyl, thiocarboxyl, carbonyl, thiocarbonyl, carboxylic acid ester, thiocarboxylic acid ester, unsubstituted or substituted amino, amide, thioamide, or Q;
• R10 and R11 are each independently H, alkyl, aryl, alkylcarbonyl, aryl carbonyl, alkylthiocarbonyl, arylthiocarbonyl, alkoxycarbonyl, aroxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl, dialkylaminocarbonyl, diarylaminocarbonyl, alkyl(aryl)aminocarbonyl, arylcarboxamido, or Q, wherein the alkyl group and the alkoxy group are each independently saturated or unsaturated, linear or branched, unsubstituted or further substituted by F, Cl, Br, I, CN, OH, alkenyl, alkynyl, alkylcarbonyl, amide, thioamide, or Q, and the aryl group is unsubstituted or optionally substituted by F, Cl, Br, I, CN, OH, alkenyl, alkynyl, alkylcarbonyl, amide, thioamide, or Q;
• R12, R13, R14, R15 and R16 are each independently H, a halogen, an amino group, a saturated or unsaturated, linear or branched, substituted or unsubstituted alkyl group , a saturated or unsaturated, linear or branched, substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group,
• or one or more of R12 in combination with R13, R14 in combination with R16, R12 in combination with R14, R12 in combination with R15, R13 in combination with R16, and R14 in combination with R15 form a 5- to 10-member ring;
• at least one of R7 in combination with R10, or R9 in combination with R11 form a saturated or unsaturated 5- to 10-member ring optionally substituted with alkyl, aryl, alkenyl, alkynyl, alkoxy, aroxyl, hydroxyl, F, Cl, Br, I, CN, nitro, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, carbonyl, thiocarbonyl, carboxylic acid, thiocarboxylic acid, carboxylic acid ester, thiocarboxylic acid ester, nitro, amino, amide, thioamide, azido, hydrazino, phosphonate, or thiophosphonate wherein the alky group and the alkoxy group are each independently saturated or unsaturated, linear or branched, substituted or unsubstituted, and wherein the aryl group is unsubstituted or substituted with F, Cl, Br, I, CN, OH, alkyl, alkenyl, alkynyl, alkoxy, aryoxy, alkylthio, arylthio, nitro, azido, hydrazino, carboxyl, thiocarboxyl, carbonyl, thiocarbonyl, carboxylic acid ester, thiocarboxylic acid ester, unsubstituted or substituted amino, amide, thioamide, or Q;
• and
• R12, R13, R14, and R16 are each independently H, a halogen, an amino group, a saturated or unsaturated, linear or branched, substituted or unsubstituted alkyl group , a saturated or unsaturated, branched or linear, substituted or unsubstituted alkoxy group , or an unsubstituted or substituted aryl group ;
• or one or more of R12 in combination with R13, R14 in combination with R16, R12 in combination with R14, R12 in combination with R15, R13 in combination with R16, and R14 in combination with R15 form a 5- to 10-member ring,
• wherein at least one of R1, R2, R6, R7R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 comprises one or more reactive groups Z independently selected from isocyanate, isothiocyanate, monochlorotriazine, dichlorotriazine, 4,6-dichloro- 1,3,5-triazines, mono- or di-halogen substituted pyridine, mono- or di-halogen substituted diazine, maleimide, haloacetamide, aziridine, sulfonyl halide, carboxylic acid, acid halide, phosphonyl halide, phosphoramidite (PO2R15NR12R13) or its thioanalogue (POSR15NR12R13), hydroxysuccinimide ester, hydroxysulfosuccinimide ester, imido ester, azido, nitrophenol ester, azide, 3-(2-pyridyl dithio)-propionamide, glyoxal, aldehyde, thiol, amine, hydrazine, hydroxyl, terminal alkene, a terminal alkyne, a platinum coordinate group and an alkylating agent.